Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/56—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having carbon atoms of carboxamide groups bound to carbon atoms of carboxyl groups, e.g. oxamides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/36—Oxalic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

• the present invention relates to a polymerizable compound which has both an alpha-ketoester group and a polymerizable double bond, and a polymer prepared therefrom.
• an alpha-ketoester group ##STR1## is a chemically active group which can be ester-exchanged with an active hydrogen containing-compound, such as an alcohol or an amine, or can be easily hydrolyzed.
• the alpha-ketoester group is introduced into a polymer, the polymer would be chemically interesting. In order to obtain such polymers, a compound which has both an alpha-ketoester group and a polymerizable double bond is required.
• EP 20,000 B1 and NL 6612666 disclose number of a compounds which have both an alpha-ketoester group and a polymerizable double bond in the form of general formula, but actually synthetic examples are very few.
• the present invention provides a novel compound which has both an alpha-ketoester group and a polymerizable double bond.
• the compound has the formula (I);
• A represent a C 1 -C 18 alkenyl, alkynyl, alkenylaryl or alkenylaralkyl group, or a group represented by: ##STR2## (wherein R 2 and R 3 , which is the same or different, represents a hydrogen atom, or a C 1 -C 5 alkyl group, Y represents an oxygen atom or --NR 4 --, in which R 4 represents a hydrogen atom or a C 1 -C 5 alkyl group, n is an integer of 1 to 5, m is an integer of 1 to 10 and l is 0 or an integer of 1 to 20);
• R 1 represents a hydrogen atom, a C 1 -C 5 alkyl group or an aryl group
• X represents an oxygen atom, a sulfur atom, --COO-- or --NR 5 --, in which R 5 is a hydrogen atom or a C 1 -C 5 alkyl group, provided that if the compound contains a Y group, X is not --NR 5 --.
• the present invention also provides a production of the above compound and polymers prepared therefrom.
• the present invention further provides a curable composition which contains the polymer obtained from the above compound.
• the polymerizable compound of the present invention can be prepared by reacting an active hydrogen-containing compound represented the formula;
• R 1 is the same as defined above and Z represents a halogen atom or --OR 1 --.
• the active hydrogen-containing compound (II) is a compound which has a hydrogen atom directly bonded to an electrophilic atom or group (e.g. oxygen, sulfur, --NR 4 -- or --COO--). Accordingly, the active hydrogen may be present in a hydroxyl group, a thiol group, an amino group or a carboxyl group.
• the group A in the active hydrogen-containing compound (II) is a group which imparts polymerizability to the compound, and includes a C 1 -C 18 alkenyl group, such as propenyl, isopropenyl, butenyl, allyl etc.; a C 1 -C 18 alkynyl, such as propynyl, butynyl etc.; a C 1 -C 18 alkenylaryl group, such as vinylphenyl, propenylphenyl etc.; a C 1 -C 18 alkenylaralkyl group, such as vinylphenylethyl, vinylphenylpropyl etc.; and a group represented by ##STR3## wherein R 2 and R 3 , which is the same or different, represents a hydrogen atom, or a C 1 -C 5 alkyl group, Y represents an oxygen atom or --NR 4 --, in which R 4 represents a hydrogen atom or a C 1 -C 5 alkyl group,
• Typical examples of the active hydrogen-containing compounds are acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, allylamine, 2-hydroxyethyl acrylate, propargyl alcohol, 2-hydroxypropyl methacrylate, p-aminostyrene, 2-hydroxypropyl acrylate, p-hydroxyethylstyrene, allylamine, propargylamine, 2-(2-hydroxyethoxy)-ethyl acrylate, 2-hydroxy-3-(2-propenyloxy)-propylacrylate, ##STR4## and the like.
• the ester compound (III) employed in the present invention includes oxalic diesters, such as dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dibutyl oxalate, diphenyl oxalate etc.; alkoxalyl halides, such as methoxalyl chloride, ethoxalyl chloride, etc.
• ester compound (III) is the alkoxalyl halide (Z is halogen)
• the reaction between the compound (III) and the compound (II) is a dehydrohalogenation reaction which quantitatively progresses.
• the reaction may be carried out at room temperature to 150° C., preferably 50° to 100° C. in an inert solvent.
• inert solvents examples include aliphatic hydrocarbons, such as pentane, hexane and heptane; aromatic hydrocarbons, such as benzene, toluene and xylene; cycloaliphatic hydrocarbons, such as cyclohexane, methylcyclohexane and decalin; petroleum hydrocarbons, such as petroleum ether and petroleum benzine; halogenated hydrocarbons, such as carbon tetrachloride, chloroform, 1,2-dichloroethane; ethers, such as ethyl ether, isopropyl ether, anisole, dioxane and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone and isophorone; esters, such as ethyl acetate, butyl acetate, propyleneglycol monoethyl ether ether
• Removal of the byproduct hydrogen chloride may be carried out by a method wherein nitrogen gas is blown into the reaction vessel, or a method wherein hydrogen chloride is reacted with a tertiary amine to form a salt of HCl which is removed out.
• the reaction compound between the compound (III) and the compound (II) is an ester exchange reaction which is generally carried out using excess dialkyl oxalate in the presence of a catalyst and a polymerization inhibitor.
• the amount of the dialkyl oxalate is 2 to 20 times, preferably 3 to 8 times larger than the molar amount of the compound (II) and the reaction temperature is within the range of room temperature to 150° C., preferably 50° to 120° C.
• the reaction may be carried out in an inert solvent as mentioned above.
• Typical examples of the catalysts are tin compounds, such as dibutyltin dilaurate, dibutyltin oxide and monobutyltin triheptate; mixture catalysts, such as dimethyltin diiodide and tetraphenylantimony iodide, dimethyltin diiodide and hexamethyl phosphoric triamide; acidic compounds, such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, chloric acid, nitric acid and boron trichloride etherate; basic compounds, such as triethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-b 7, pyridine sodium methoxide, sodium ethoxide and t-butoxypotassium hexamethylphosphoric triamide, metal oxides or metal salts,
• Typical examples of the polymerization inhibitors are hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4-t-butylcatechol, bisdihyroxybenzylbenzene, 2,2'-methylenebis(6-t-butyl-3-methylphenol), 4,4'-thiobis(6-t-3-methylphenol), p-nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt, dithiobenzylsulfide, p,p'-ditolyltrisulfide, p,p'-ditolyltetrasulfide, dibenzyltetrasulfide, tetraethylthiuramsulfide and the like.
• the obtained product may be purified by distillation, crystallization, etc. Distillation is generally effected at a reduced pressure (from atmospheric pressure to 0.01 mmHg) at a temperature of room temperature to 180° C., preferably 50° to 120° C. in the presence of zeolite or with stirring.
• the obtained polymerizable compound of the present invention can be polymerized solely or with a copolymerizable compound.
• Polymerization may be carried out at a temperature of 50° to 150° C., preferably 70° to 120° C., in the inert solvent mentioned above in the presence of a polymerization initiator.
• Typical examples of the polymerization initiators are azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, tetramethyltiuramdisulfide, 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile, acetylcyclohexylsulfonyl peroxide, 2,2'-azobis(2,4-dimethylvaleronitrile) and the like.
• the copolymerizable compound employed in the present invention includes mono-olefins or di-olefins, such as styrene, alpha-methylstyrene, alpha-ethylstyrene, 2-methyl-1-butene, ethylene, propylene, butylene, amylene, hexylene, butadiene-1,3, isoprene etc.; halogenated mono-olefins or di-olefins, such as alpha-chlorostyrene, alpha-buromostyrene etc.; organic or inorganic esters, such as vinyl acetate, vinyl propionate, vinyl butylate, vinyl banzoate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, hexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, allyl chloride, allylcyanamide, allyl a
• unsaturated amides such as acrylamide, methacrylamide, crotonamide etc.
• unsaturated sulfonic acids or salts thereof such as 2-sulfoethyl acrylate, p-vinylbenzenesulfonic acid etc.
• the polymer (or copolymer) of the present invention has at least two alpha-ketoester groups which are reactive with other active hydrogen-containing groups, particularly a hydroxyl group. Accordingly, the polymer may be combined with a compound having at least two hydroxyl groups, i.e. polyhydroxyl compound, to form a curable composition.
• the curable composition has excellent properties in low temperature curing ability and acid resistance.
• the polyhydroxyl compound includes polyhydric alcohols, polyester polyols, polyether polyols, polyurethane polyols, polyvinyl alcohols, phenol resins, hydroxyl-containing polybutadine, hydroxy-containing polychloroprene, ring-opened epoxy resins, polyorganosiloxane and the like.
• Typical examples of the polyhydric alcohols are 3-allyloxy-1,2-propane diol, 2,2-bis(chloromethyl)-1,3-propane diol, 2-bromo-2-nitro-1,3-propane diol, 3-bromo-1,2-propane diol, butane diol, butyne diol, cyclohexane diol, cyclooctane diol, cyclopentane diol, decalin diol, decane diol, ethylene glycol, propylene glycol, dihydroxyacetophenone, dihydroxyanthraquinone, dihydroxybenzophenone, hydroxybenzylalcohol, catechol, pentaerythritol, glycerol, amylose, lactose, sucrose, manitol, maltose and the like.
• the acryl polyol is a polymer of a hydroxyl containing ethylenically unsaturated monomer.
• examples of the hydroxy containing unsaturated monomers are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and the like.
• the acryl polyol may be a copolymer of the above mentioned monomers with other monomers.
• Examples of the other monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ethylhexyl (meth)acrylate, alpha-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, dimethylaminoethyl (meth)acrylate, and the like.
• polyester polyols are a condensate of a polyhydric alcohol as mentioned above and a polybasic acid or an anhydride thereof (e.g. phthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid etc.); a reaction product of a polyhydric alcohol as mentioned above with an epoxy compound (e.g.
• an alkyd polyol a product of a polyhydric alcohol and oil (e.g. soybean oil and safflower oil)
• a ring open product of ⁇ -caprolantone and the like.
• polyether polyols examples include an adduct of a polyhydric alcohol as mentioned above and an alkylene oxide (e.g. ethylene oxide, propylene oxide, tetrahydrofuran etch) and the like.
• alkylene oxide e.g. ethylene oxide, propylene oxide, tetrahydrofuran etch
• the polyurethane polyol may be prepared by reacting a polyol as mentioned above and a polyisocyanate compound.
• the polyisocyanate compounds are ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, diisocyanatodimethylxylene, diisocyanatodiethylxylene, lysine diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), ⁇ 4,4'-ethylenebis(cyclohexylisocyanate), alpha, alpha'-diisocyanato-1,3-dimethylbenzene, alpha, alpha'-diisocyanato-1,4-dimethylbenzene, isophorone diis
• phenol resins examples include novolac or resol type phenol resin, rosin modified phenol resin, alkylphenol resin, butylated resol resin, allyl ether resol resin and the like.
• the polyorganosiloxane polyol includes a polymer or cyclic compound having both alkylhydroxyalkylsiloxy unit and dialkylsiloxy unit or(and) diphenylsiloxy unit, ⁇ , ⁇ -bis(hydroxyalkyl)polydimethylsiloxane and the like.
• Typical examples of the polyols are ##STR5##
• the curable composition of the present invention may generally contain a catalyst as mentioned in the synthesis of the polymerizable compound.
• the catalyst may be present in the composition in an amount of 0.0001 to 10% by weight, preferably 0.001 to 5% by weight based on the total amount of the poly(alpha-ketoester) and the polyhydroxyl compound.
• the curable composition may contain a solvent is necessary.
• the solvent can be the inert solvent as mentioned above, but alcohols (e.g. ethylene glycol, 2-ethylhexanol, t-butanol, n-hexanol, n-butanol, cyclohexanol, isopropanol, n-propanol, benzyl alcohol, ethanol, methanol etc.) may be employed.
• the solvent may be present in the composition in an amount of 0.01 to 90% by weight, preferably 0.5 to 80% by weight, but alcohols are preferably 50% by weight or less because they are ester-exchanged with alkoxalyl ester.
• the curable composition may be cured at a temperature of 70° to 200° C., preferably 90° to 180° C. for 5 minutes to 2 hours, preferably 10 minutes to one hour.
• the polymerizable compound and polymer of the present invention have the alpha-ketoester group which can be ester-exchanged with an active hydrogen containing-compound, such as an alcohol or an amine, or can be easily hydrolyzed.
• the polymer may be suitable for coating, adhesive, plastics, fiber and the like.
• the polymer may be combined with another active hydrogen containing compound to form a curable composition.
• the composition is suitable for the field of coating or adhesive.
• Ethylpropargyl oxalate was obtained as generally described in Example 9, with the exception that 50 g (1 mol) of propargyl alcohol, 438 g (3 mol) of diethyl oxalate and 3 g of p-toluenesulfonic acid were employed.
• Ethylmethacryloyl oxalate was obtained as generally described in Example 9, with the exception that 86 g (1 mol) of methacrylic acid, 438 g (3 mol) of diethyl oxalate and 3 g of p-toluenesulfonic acid were employed.
• 2-Ethoxalyloxyethyl methacrylate was obtained as generally described in Example 9, with the exception that 130 g (1 mol) of 2-hydroxyethyl methacrylate, 438 g (3 mol) of diethyl oxalate and 3 g of p-toluenesulfonic acid were employed.
• 2-Ethoxalyloxyethyl acrylate was obtained as generally described in Example 9, with the exception that 116 g (1 mol) of 2-hydroxyethyl acrylate, 438 g (3 mol) of diethyl oxalate and 3 g of p-toluenesulfonic acid were employed.
• N-Propargylethyl oxalate was obtained as generally described in Example 14, with the exception that 56 g (1 mol) of propargylamine and 146 g (1 mol) of diethyl oxalate were employed.
• a 500 ml flask equipped with a decanter, a thermometer, a stirrer and an inlet for nitrogen gas was charged with 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate and 365.4 g (2.5 mol) of diethyl oxalate, to which 2 g (10 mmol) of p-toluenesulfonic acid (catalyst) and 4 g of hydroquinone (polymerization inhibitor) were added.
• the mixture was heated to keep 120° C. for 4 hours in nitrogen atmosphere with distilling 14 mol (0.25 mol) of ethanol away.
• a 500 ml flask equipped with a decanter, a thermometer, a stirrer and an inlet for nitrogen gas was charged with 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate and 365.4 g (2.5 mol) of diethyl oxalate, to which 2 g (10 mmol) of p-toluenesulfonic acid (catalyst) and 4 g of 2-t-butylhydroquinone (polymerization inhibitor) were added.
• the mixture was heated to keep about 130° C. for 3 hours in nitrogen atmosphere with distilling 22 ml (0.38 mol) of ethanol away.
• a 500 ml flask equipped with a decanter, a thermometer, a stirrer and an inlet for nitrogen gas was charged with 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate and 365.4 g (2.5 mol) of diethyl oxalate, to which 2 g (10 mmol) of p-toluenesulfonic acid (catalyst) and 4 g of 2,5-di-t-butylhydroquinone (polymerization inhibitor) were added.
• the mixture was heated to keep about 130° C. for 3 hours in nitrogen atmosphere with distilling 23.5 ml (0.40 mol) of ethanol away.
• a 500 ml flask equipped with a decanter, a thermometer, a stirrer and an inlet for nitrogen gas was charged with 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate and 365.4 g (2.5 mol) of diethyl oxalate, to which 2 g (10 mmol) of dibutyltin dilaurate (catalyst) and 4 g ob 2,5-di-t-butylhydroquinone (polymerization inhibitor) were added.
• the mixture was heated to keep it at about 120° C. for 2 hours in nitrogen atmosphere with distilling 32.5 ml (0.56 mol) of ethanol away.
• a 100 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 13.1 g of xylene and heated to 120° C.
• a 100 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 15.0 g of xylene and heated to 130° C.
• a 100 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 15.0 g of xylene and heated to 130° C.
• a one liter flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 180.0 g of butyl acetate and heated to 120° C.
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 21.8 g of xylene and heated to 135° C.
• 6.3 g of Kaya Ester-O and 6.3 g of xylene were added dropwise for 3 hours.
• 0.63 g of Kaya Ester-O and 5.0 g of xylene were added dropwise for one hours.
• the polymer solution has a viscosity of 326 (E type viscometer at 25° C.) and a nonvolatile content of 70% (130° C., 30 minutes).
• One of the products (curing agent) prepared in Examples 28 to 33 and the acryl polyol of Production Example 2 were mixed with 1 wt %/solid content of dibutyltin dilaurate.
• the resultant composition was coated on a tin plate by a bar coater No. 40, and then baked at 130° or 150° C. for 30 minutes. Curing properties were evaluated and the results where shown in Table 3.
• a catalyst was mixed with 8.51 g of the 2-ethoxalyloxy methacrylate copolymer prepared in Example 21 and 6.49 g of the acryl polyol of Production Example 1 in an amount ratio of catalyst/resin solid content of 1 wt % to form a resin composition.
• the catalyst was selected from dibutyltin dilaurate (DBTL), diazabicyclooctane (DABCO) and p-toluenesulfonic acid monohydrate (PTS).
• DBTL dibutyltin dilaurate
• DABCO diazabicyclooctane
• PTS p-toluenesulfonic acid monohydrate
• Another resin composition which did not contain any catalyst was prepared.
• the resin composition was coated on a tin plate by a bar coater in a thickness of 20 microns, and then baked at 110°, 130°, 150° or 180° C. for 30 minutes. Curing properties were evaluated and the results
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with xylene and n-butanol in an amount shown in the initial charge column of Table 5 and heated to a polymerization temperature.
• a monomer mixture shown in Table 5 and Kaya Ester-O were added dropwise for 3 hours.
• Kaya Ester-O and xylene were added dropwise in amounts shown in the after shot column of Table 5 for one hour.
• the obtained polymer solution was transparent and light yellow. Its molecular weight, nonvolatile content and viscosity are shown in Table 6.
• One of the resins of Examples 36 to 38 was mixed with an amount of 1 wt %/resin solid content of dibutyltin dilaurate to form a resin composition.
• the resultant composition was coated on a tin plate by a bar coater No. 40, and then baked at 130° or 150° C. for 30 minutes. Curing properties were evaluated and the results were shown in Table 7.
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 40 g of xylene and heated to 120° C.
• 9 g of Kaya Ester-O were added dropwise for 3 hours.
• 1 g of Kaya Ester-O and 10 g of xylene were added dropwise for one hour. After mixing with heating for 1.5 hours, it was heated to remove 30 g of xylene.
• the obtained solution was cooled to room temperature to obtain transparent and light yellow polymer.
• the polymer solution had a viscosity of 416 cps (E type viscometer at 25° C.) and a nonvolatile content at 70% (130° C., 30 minutes).
• Example 40 The resin of Example 40 was mixed with an amount of 1 wt %/resin solid content of a catalyst shown in Table 8. The resultant composition was coated on a tin plate by a bar coater No. 40, and then baked at 130° or 150° C. for 30 minutes. Curing properties were evaluated and the results were shown in Table 8.
• a mixture was prepared by dissolving 52.1 g (0.4 mol) of hydroxyethyl methacrylate and 40.5 g (0.4 mol) of triethylamine in 250 ml of benzene and cooled to 2° C. To the content, a solution of 65.8 g (0.4 mol) of t-butoxalyl chloride in 200 ml of benzene was added dropwise for 3 hours while precipitating salt. After the completion of dropping, it was allowed to stand for 30 minutes without cooling to terminate reaction.
• a 500 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 90 g of xylene and heated to 100° C.
• 39.0 g of t-butoxalyloxyethyl methacrylate of Example 42 26.2 g of n-butyl acrylate, 34.8 g of methyl methacrylate and 2.0 g of azobisisobutylonitrile were added dropwise for 3 hours.
• 0.2 g of azobisisobutylonitrile and 10 g of xylene were added dropwise for one hour.
• Example 42 As generally described in Example 42, the reaction was conducted with the exception that 46.4 g (0.4 mol) of 2-hydroxyethyl acrylate was employed instead of 2-hydroxyethyl methacrylate to obtain 96.6 g (yield 98.8%) of t-butoxalyloxyethyl acrylate which was identified by IR and NMR.
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 45 g of xylene and heated to 100° C.
• 36.6 g of t-butoxalyloxyethyl acrylate of Example 44 7.7 g of n-butyl acrylate, 5.7 g of methyl methacrylate and 1.0 g of azobisisobutylonitrile were added dropwise for 3 hours.
• 0.1 g of azobisisobutylonitrile and 5 g of xylene were added dropwise for 30 minutes.
• a mixture was prepared by dissolving 92.6 g (0.5 mol) of SIPOMER TBM (t-butylaminoethyl methacrylate available from Arcolac Company) and 50.6 g (0.5 mol) of triethylamine in 400 ml of benzene and cooled to 2° C. A solution of 68.3 g (0.5 mol) of ethoxalyl chloride in 100 ml of benzene was added dropwise for one hour. After the completion of dropping it was allowed to mix for 1.5 hours without cooling to terminate reaction.
• SIPOMER TBM t-butylaminoethyl methacrylate available from Arcolac Company
• the precipitated salt was filtered off and the filtrate was evaporated to obtain brown viscous liquid which was identified by IR and 1 H-NMR to find N-t-butyl-N-ethoxalylaminoethyl methacrylate.
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 35 f of xylene and heated to 135° C.
• 60.0 g of N-t-butyl-N-ethoxalylaminoethyl methacrylate of Example 46 20.0 g of isobutylmethyl methacrylate, 10.0 g of styrene, 10.0 g of alpha-methylstyrene dimer and 10.0 g of Kaya Ester-O were added dropwise for 3 hours. After mixing for 30 minutes, 1.0 g of Kaya Ester-O and 8 g of xylene were added dropwise for one hour.
• a 200 ml flask equipped with a decanter, a condenser, a stirrer and a dropping funnel was charged with 50 ml of xylene and heated to 110° C.
• To the content 52.2 f of isopropoxalyloxyethyl methacrylate, 27.8 g of cyclohexyl methacrylate, 10.0 g of styrene, 10.0 g of alpha-methylstyrene dimer and 10.0 g of t-butylperoxy-2-ethyl hexanate were added dropwise for 3 hours. After mixing at 110° C.

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• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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• 1989
  • 1989-12-07 JP JP1318504A patent/JP2564409B2/ja not_active Expired - Lifetime
• 1990
  • 1990-01-11 CA CA002007579A patent/CA2007579A1/en not_active Abandoned
  • 1990-01-12 DE DE69014912T patent/DE69014912T2/de not_active Expired - Fee Related
  • 1990-01-12 EP EP90300352A patent/EP0378429B1/en not_active Expired - Lifetime
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